Halogenated thioethers and method of preparations

ABSTRACT

New halogenated thioether compounds of the general formula R (SCH2-CHY-CH2X)n IN WHICH X represents a halogen atom, Y represents a hydrogen atom or a hydroxyl group, R is a mono or divalent cyclic or acyclic unsaturated hydrocarbon residue having up to 20 carbon atoms and n is 1 or 2 according to whether R is mono or divalent, are prepared by reacting thietane (thiacyclobutane or trimethylene sulphide) or 3-hydroxy thietane with a double-bonded halogen-substituted hydrocarbon derivative. By means of treatment with an aqueous solution of a base, the new thioether compounds in which Y is hydroxyl may be used to prepare corresponding new 2,3-epoxy-thiopropyl and bis(2,3-epoxy-thiopropyl) compounds.

States atent Esclamadon 5] June 27, 1972 l HALOGENATED THIOE li RSPrimary Examiner-Joseph Rebold METHOD OF PREP TIQNS AssistantExaminerDelbert R. Phillips Attorney-Ostrolenk, Faber, Gerb & Soffen[72] Inventor: Christian Esclamadon, Les Chenes,

France [73] Assignee: Societe Anonyme dite: Societe Nationale desPetroles DAquitaine Courbevoie [57] ABSTRACT 22 Filed: May 20, 1969 Newhalogenated thioether compounds of the general formula [211 App]. No..826,291 R(S CH2 CHY CHZX)YI [30] Foreign Application p i Data in which Xrepresents a halogen atom, Y represents a hydrogen atom or a hydroxylgroup, R is a mono or divalent May 21, 1968 France ..68152543 cyclic oracyclic unsaturated hydrocarbon residue having up May 21, 1968 France..68152544 to 20 Carbon atoms and n is 1 or 2 according to whether R ismono or divalent, are prepared by reacting thietane (thia- [52] US. Cl..260/609 A, 106/287 SC, 260/47 EP, cyclobutane or ni th lene ul hide)or 3-hydroxy thietane 260/79 260/3486, 260/348 R, 260/481 R, with adouble-bonded halogen-substituted hydrocarbon 260/593 H, 260/609 E,260/609 F, 424/ derivative. By means of treatment with an aqueoussolution of [51 Int. Cl ..C07c 149/00, C07c 149/18 3 base, the newthioether compounds i which Y is hydroxyl [58] Field of Search ..260/609A may be used to prepare corresponding new thio ro land bis(2,3-eoxy-thiopro 1) compounds. [5 6] References Cited p py P W OTHERPUBLICATIONS Truce et al. J. Org. Chem. Vol. 33 (1968) pp. 43- 47 21Claims, No Drawings HALOGENATED THIOETHERS AND METHOD OF PREPARATIONSThe present invention relates to a new process for the preparation ofhalogenated thioethers, which may be hydroxylated; it relatesparticularly to the synthesis of these compounds starting from halogenderivatives and thietane or 3- hydroxy-thietane, which are readilyavailable starting materials. The compound referred to as thietane isthiacyclobutane (trimethylene sulphide).

The invention also relates to certain new thioethers.

The products prepared by the process of the present invention can berepresented by the general formula:

in which X represents a halogen atom, preferably chlorine or bromine, Ya hydrogen atom or a hydroxyl group, R is a mono or divalent hydrocarbonresidue which may be unsaturated and cyclic or not and which may includean ester function or ketone function and be substituted with a halogen,and n is an integer equal to 1 or 2 according to whether R is mono ordivalent. 7

These compounds are of importance industrially in different fields. Onaccount of the presence in the same molecule of heteroatoms such assulphur, halogen and possibly oxygen, and one or more double bonds, theyare particularly reactive.

They are used in the preparation of insecticides or pesticides. They canalso be used in the composition of plasticizers for sulphur. Moreover,those thioethers prepared by the process of the invention which have ahalogen in the alphaposition relative to a hydroxyl group can readily betransformed by dehydrohalogenation into epoxy derivatives of sulphurcorresponding to the formula:

These epoxy derivatives enable epoxy resins to be obtained by theaddition of, for example, polyamines or carboxylic polyacids; they canalso be used as modifiers for commercially available epoxy resins.

The process according to the invention consists in reacting a mono ordihalogenated hydrocarbon derivative in which the carbon atom which isin the alpha-position relative to that to which the halogen is attachedcarries a double bond, with thietane or 3-hydroxy-thietane.

The reaction according to the invention can be represented y R, Y and nhaving the meanings given above.

In the course of this reaction, there is cleavage of the heterocyclicsulphur ring at the position of the sulphur atom, attachment of theR-group of the halogenated derivative to the sulphur atom and attachmentof the halogen to the hydrocarbon residue of the cleaved heterocyclicsulphur ring.

When dihalogenated derivatives are used, a mixture of mono-addition anddi-addition compounds is formed, these being respectively RSCH -CHYCH Xand XI-I C CHYCI-I SRSCH --CHYCH X The halogenated hydrocarbonderivatives which have a double bond on the carbon which is thealpha-position relative to that which carries the halogen, and which areused for preference in the process according to the invention, can berepresented by the following general formula:

in which X represents a halogen atom, preferably chlorine or bromine, R,represents a hydrogen atom or a hydrocarbon radical which may besubstituted or unsubstituted and have up to 12 carbon atoms, p is zeroor 1 and R represents oxygen or a divalent hydrocarbon radical having upto 12 carbon atoms, it being possible for this radical and R, to bejoined and to form with the carbon atom to which they are attached, anunsaturated cyclic hydrocarbon ring, the said radical R or the said ringpossibly also being substituted by a CH,X group attached to a carbonwhich carries a double bond.

The radical R, may be a substituted or unsubstituted alkyl radical suchas methyl, ethyl, propyl, hexyl or octyl, a substituted or unsubstitutedaryl radical such as phenyl, toluyl or trimethylphenyl, or a cycloalkylradical such as cyclopentyl, cyclohexyl or cyclooctyl.

The divalent hydrocarbon radical R can be saturated or unsaturated andmay have a halomethyl substituent. In particular, it can represent asubstituted or unsubstituted alkylidine radical such as ethylidene,propylidene, pentylidene, hexylidene, benzylidene or 2-halo-ethylidene,for example.

The radicals R, and R can form with the carbons to which they areattached, various unsaturated cyclic groups and, in particular,hydrocarbon cyclic groups having an aromatic nucleus, which cyclicgroups can include a halo-methyl substituent.

By way of example, reference may be made to allyl chloride or bromide,2-methyl-3-chloro or Z-methyl-3-bromo-propene, transl ,4-dichloro ordibromo-2-butene, benzyl chloride, 1,4- dichloromethyl-benzene andmethyl, ethyl, propyl, n-hexyl or phenyl chloro or bromo-acetate.

In order to carry out the reaction, a mixture of the halogen derivativeand the thietane or hydroxy-thietane is heated. The temperature of thereaction depends on the halogen derivative which is used but it isgenerally between 50 and 120 C. In the case in which 3-hydroxy-thietaneis reacted with a halogen derivative of the formula in which Rrepresents a hydrocarbon radical as previously defined, the reactiontemperature will always be less than C. The reactants can be used instoichiometric proportions but it is preferable to use one or other inslight excess, and in particular, to use an excess of the more volatilereactant.

Generally speaking, the reaction takes place without a catalyst but theuse of a small quantity of a tertiary aliphatic amine allows the speedof the reaction to be increased.

Among other factors, the duration of the reaction depends on the natureof the halogen derivative used and on the presence or absence of acatalyst. Generally the reaction proceeds for 12 to 24 hours in theabsence of a catalyst and 12 to 20 hours in the presence of a catalyst.

When the reaction has been completed, the reactants which have notreacted are separated and the thioethers according to the invention arecollected.

The halogenated and hydroxylated thioethers which can be obtained by theprocess according to the invention readily yield the corresponding epoxyderivatives by treatment with an aqueous solution of sodium or potassiumhydroxide according to the reaction:

The group SCII,CIICII,

2 .r as r r i e it d by infra-red spectrography, by means of theabsorption bands at the following frequencies:

3,060 cm, 1,480l,475 cm,

1,260 cm", 920 cm", 840 cm The following non-limitative examplesillustrate the invention. EXAMPLE 1 Oil is obtained with a yield of 70percent relative to the thietanol.

This is a new chemical product boiling at 88 C under 0.2 mm Hg.

The characteristics of this product are as follows: Refractive index n1.5230 lts elementary analysis is:

C "70 H S Cl Found 43.53 6.72 18.64 21.36 Calculated 43.28 6.61 19.221.37

Dehydrochlorination of the chlorhydrin obtained 150 g. of allyl3-chloro-2-hydroxy-propyl sulphide are dissolved in 250 cc. of ether;this solution is treated with 250 g. of 40 percent sodium hydroxidesolution for 45 minutes and the mixture is filtered and separated; theaqueous phase is extracted with ether. Allyl 2,3-epoxy-propyl sulphideor 0 allyl glycidyl sulphide CllF C11(J1I SCl12-C11-CII is obtained witha yield of 43 percent relative to the 3-hydroxy thietane.

The characteristics of this product are: Boiling point 65 C under 5 mmof mercury. n 1 .500 1 EXAMPLE 2 In the reaction vessel as previouslythere are mixed by means of an agitator, 92 g. (1 mole) of2-methyl-3-chloropropene and 90 g. (1 mole) of 3-hydroxy-thietane; themixture is heated for 24 hours at a temperature of 70 C while continuingthe agitation. The sulphuretted chlorohydrin is distilled 45 andobtained with a yield of 60 percent.

The formula of this new compound is:

CIIQ CCIIgSCI'I CIICII CI I C H3 0 II and its characteristics are asfollows: Boiling point 92 C under 0.25 mm of mercury n,, c= 1.5141

Its elementar anal is is C H S Cl 70 found 47.29 7.85 20.17 17.09calculated 47.22 7.75 20.17 17.21

Preparation of the epoxy derivative By dehydrochlorination of thehalohydrin obtained and under the same conditions as previously thecorresponding epoxy derivative cm:ccH2-scH:0H-cm CH 0 is obtained with ayield of 40 percent.

This is a new product whose boiling point is: 53 C under 0.15 mm Hg. Itselementary analysis is:

C H S 70 found 58.4 8.56 21.37

calculated 58.33 8.33 22.2

EXAMPLE 3 A mixture of 150 g. (1.2 mole) of benzyl chloride and g. (1mole) of 3-hydroxy-thietane is heated for 20 hours at a temperature of Cwhile stirring. The reaction product is distilled under reducedpressure.

is obtained with a yield of 53 percent relative to the thietanol.

The physical constants are: n 1 .5 790 Boiling point C under 0.05 mm Hg.Dehydrochlorination of the sulphuretted chlorhydrin An ether solution ofthe chlorhydrin obtained is treated with a 40 percent aqueous solutionof sodium hydroxide; the product obtained is filtered and separated; thesolvent in the organic phase is distilled and benzyl 2,3-epoxy-propylsulphide is obtained with a yield of 42 percent.

The characteristics of this new product are as follows: Boiling point100 C under 0.5 mm of mercury c= 1.5660

The same compound can be prepared under the same conditions startingfrom benzyl bromide.

The analysis of this epoxy sulphur compound is as follows:

C H S found 6624 6.95 17.69 calculated 66.65 6.66 17.79

EXAMPLE 4 In a 500 cc. reaction vessel, 136 g. (1.1 mole) of ethylchloroacetate and 50 g. (1.58 mole) of 3-hydroxy-thietane are mixed. Themixture is heated for 24 hours at 80 C while stirring; the unreactedsubstances are distilled and 79 g. (that is to say 62 percent) of thecorresponding chlorhydrin are obtained: ethyl 6-chloro-5-hydroxy-3-thiahexanoate This compound, which has not previously been described, hasthe following characteristics: Boiling point 140 C under 0.4 mm ofmercury c= 1.5022

Its elementary analysis is:

C H S Cl found 39.15 5.70 17.50 14.35 calculated 39.45 6.12 16.70 15.03

EXAMPLE 5 A mixture of 125 g. (1 mole) of trans-1,4-dichloro-2-buteneand 220 g. (3 moles) of 3-hydroxy-thietane are heated for 12 hours at atemperature of 80 C. The mixture is stirred throughout the reaction. Theexcess 3-hydroxy-thietane is distilled under vacuum. The crude productcontains a mixture of the sulphuretted dichlorhydrins of the formulas:

The chlorhydrin (4) is separated by distillation and 175 g of thesulphuretted dichlorhydrin (5 in solution in ether is treated with a 40percent solution of sodium hydroxide for 45 minutes while stirringvigorously. The medium is filtered and separated; the organic solvent isdistilled under vacuum; the residue is dried by means of anhydroussodium sulphate. trans- ,4-bis-( 2,3-epoxy-propylthio )-2-buteneC1IrCHCH2SCHrCH=CHCHzS-CH2-CH CH2 is obtained with a yield of 80 percentrelative to the dichloro derivative used.

The characteristics of this crude non-distillable product are asfollows:

C H S found 49.35 6.83 28.60 calculated 51.72 6.89 27.71

lts infra-red spectrum corresponds to the formula given. EXAMPLE 6 Amixture of 250 g. (1.43 mole) of 1,4-dichloromethylbenzene and 260 g.(2.9 moles) of 3-hydroxy-thietane is heated for 2 hours at 100 C. Thecorresponding di-sulphuretted dihalochlorhydrin is obtained C1 OH 2 125cc. of acetone is added directly to the reaction product and the mixtureis treated with 30 g. of 40 percent sodium hydroxide solution. Themixture is stirred vigorously for 30 minutes, filtered and separated.After evaporation of the solvent 270 g. of the corresponding diepoxydisulphuretted derivative are obtained.

EXAMPLE 7 A mixture of 74 g. (1 mole) of thietane and 150 G. (2 moles)of allyl chloride is introduced into a 500 cc. autoclave and is heatedwith stirring at a temperature of 120 C under autogenous pressure for 24hours.

The contents of the autoclave are then distilled and 100 g. of allyl3-chloro-propyl sulphide CH CH-CH S(CH Cl is obtained with a yield of 67percent.

This is a new chemical product whose boiling temperature is 55 C under0.3 mm Hg and its refractive index is I u l .4990 EXAMPLE 8 A mixture of91.5 g. (1 mole) of mcthallyl chloride and 74 g. 1 mole) of thietane isheated with stirring for 16 hours at a temperature of 70 C in thepresence of a catalytic quantity of tributyl amine.

The reaction mixture is then distilled under reduced pressure; in thisway 68 g. of methallyl 3-chloro-propyl sulphide is obtained with a yieldof 40 percent.

This is a new chemical product whose characteristics are as follows:Boiling temperature 48 C under 0.05 mm Hg Refractive index n,, 1.4972Its elementary analysis is:

C H S Cl found 51.22 7.65 18.11 21.50 calculated 51.06 7.90 19.46 21.58

EXAMPLE 9 A mixture of 125 g. (1 mole) of trans-l ,4-dichloro-2-buteneand 148 g. (2 moles) of thietane is kept for 24 hours at a temperatureof 70 C with stirring.

Distillation of the reaction mixture enables a new dihalogenatedthioether to be obtained, trans-1,8-dichloro-5- thia-2-octene Thisproduct is characterized as follows:

Boiling temperature 105 C under 0.1 mm Hg n 1.5251

Elementary analysis C H S Cl found 42.96 6.25 16.55 35.17 calculated42.21 6.03 16.08 35.68

The distillation residue contains the diaddition derivative A mixture of126.5 g. (1 mole) of benzyl chloride and 74 g. 1 mole) of thietane isheated at a temperature of 70 C for 24 hours with continuous stirring.

When the reaction has been completed the reaction mixture is distilled;in this way, benzyl 3-chloro-propyl sulphide C l-l CH- ,S-(CH C1 isobtained with a yield of 50 percent.

EXAMPLE 11 A mixture of 92.5 g. (1 mole) of chloropropanone and 74 g. (1mole) of thietane is kept for 24 hours at a temperature of 60 C. withstirring.

Distillation of this reaction mixture enables 1-chloro-4-thiaheptanoneto be obtained with a yield of 67.5 percent.

This is a new product which possesses the following characteristics:Boiling temperature 73 C under 0.03 mm Hg m, l .53 52 Elementaryanalysis gives:

C H S Cl found 43.60 6.84 18.40 21.47 calculated 43.25 6.60 19.20 21.30

EXAMPLE 12 A mixture of 122 g. (1 mole) of ethyl chloroacetate and 74 g.1 mole) of thietane is kept at a temperature of C for 24 hours withstirring.

Distillation of the reaction mixture yields ethyl l-chloro-4-thia-hexanoate This product possess the following characteristics:Boiling temperature C under 0.15 mm Hg n 1.48 32 wherein Y is hydrogenor hydroxyl, with a halogenated hydrocarbon derivative of the formulawherein X is halogen, p is or 1, R is hydrogen or a hydrocarbon radicalhaving up to 12 carbon atoms selected from the group consisting ofalkyl, aryl or cycloalkyl radicals, and R is an unsubstituted orhalomethyl substituted alkylidine radical of up to 12 carbon atoms, andwherein R and R can, together with the carbon atom to which they areattached, form an unsubstituted or halomethyl substituted aromatic ring.

2. A process according to claim 1, wherein in said hydrocarbonderivative, R is a halomethyl substituted alkylidine radical.

3. A process according to claim 1, wherein said hydrocarbon derivativeis of the formula in which X represents a halogen atom, p is zero or 1and R and R are joined and, together with the carbon atom to which theyare attached, form an unsubstituted or halomethyl substituted aromaticring.

4. A process according to claim 3, wherein one of the carbon atoms ofsaid ring carries a halomethyl substituent.

5. A process according to claim 1, wherein said halogen substituent ischlorine.

6. A process according to claim 1, wherein said halogen substituent isbromine.

7. A process according to claim 1, which is carried out at a reactiontemperature between 50 and 120 C.

8. A process according to claim 1, wherein whichever of said thietanecompound and said hydrocarbon derivative is the more volatile, is usedin excess, relatively to the stoichiometric quantity.

9. A process according to claim 1, which proceeds for from 12 to 24hours in the absence of a catalyst.

10. A process according to claim 1, wherein an aliphatic tertiary amineis used as a catalyst and said process proceeds for from 12 to 20 hours.

11. A halogenated thioether compound selected from the group consistingof wherein X is halogen, p is 0 or 1, R is hydrogen or a hydrocarbonradical having up to 12 carbon atoms selected from the group consistingof alkyl, aryl or cycloalkyl radicals, R is an unsubstituted orhalomethyl substituted alkylidine radical of up to 12 carbon atoms, andwherein R and R can, together with the carbon atom to which they areattached, form a halomethyl substituted aromatic ring, Y is hydrogen orhydroxy R(SCH -CHY-CH X) (2) wherein X is halogen and R is -CH C H,,CHor CH CH CH-CH Y is hydrogen or hydroxy and C H CH -SCH CHOHCH X. (3)12. A compound according to claim 11 wherein X is chlorine.

13. A compound according to claim 11, wherein X is bromine.

14. A compound of the formula CH2=C-CHz-SCHCH2C1 lHg H in accordancewith claim 1 l.

15. A compound of the formula C H -CH SCH CHOHCH Cl in accordance withclaim 1 l.

16. Methallyl 3-chloro-propyl sulfide in accordance with claim 11.

17. l,8-dichloro-5-thia-2-octene in accordance with claim 1 1.

18. A halogenated thioether according to claim 11 wherein Y is hydrogen.

19. A halogenated thioether compound according to claim 1 1 wherein Y is01-1.

20. A process for the preparation of allyl 3-chloro-2- hydroxy-propylsulphide, which comprises reacting allyl chloride and 3-hydroxy-thietaneand recovering the sulphide 5 product therefrom.

21. Allyl 3-chloro-2-hydroxy-propyl sulphide.

22% UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PatentNo.-3,673 260 Dated June 27 1972 Inventor) Christian E sclamadon It iscertified that error appears 1n theabove-identified patent and that saidLetters Patent are hereby corrected as shown below:

r Column 4; line 67, for "formulas" read.

formulae Column 8, line 6', read (l) before the formula and delete "(1)"afterthe formula; line 18, read (2) before the formula and delete "(2)"after the formula; line 21 read (3) before the formula and delete "(3)"after the formula. v I

Signed and sealed this 26th day of December 1972.

SEAL) ATbesi:

ROBERT GO TSCHALK Commissioner of Pa ienlfs EDWARD IIUFLEICETER IR.Art-meshing Officer

2. A process according to claim 1, wherein in said hydrocarbonderivative, R2 is a halomethyl substituted alkylidine radical.
 3. Aprocess according to claim 1, wherein said hydrocarbon derivative is ofthe formula in which X represents a halogen atom, p is zero or 1 and R1and R2 are joined and, together with the carbon atom to which they areattached, form an unsubstituted or halomethyl substituted aromatic ring.4. A process according to claim 3, wherein one of the carbon atoms ofsaid ring carries a halomethyl substituent.
 5. A process according toclaim 1, wherein said halogen substituent is chlorine.
 6. A processaccording to claim 1, wherein said halogen substituent is bromine.
 7. Aprocess according to claim 1, which is carried out at a reactiontemperature between 50* and 120* C.
 8. A process according to claim 1,wherein whichever of said thietane compound and said hydrocarbonderivative is the more volatile, is used in excess, relatively to thestoichiometric quantity.
 9. A process according to claim 1, whichproceeds for from 12 to 24 hours in the absence of a catalyst.
 10. Aprocess according to claim 1, wherein an aliphatic tertiary amine isused as a catalyst and said process proceeds for from 12 to 20 hours.11. A halogenated thioether compound selected from the group consistingof wherein X is halogen, p is 0 or 1, R1 is hydrogen or a hydrocarbonradical having up to 12 carbon atoms selected from the group consistingof alkyl, aryl or cycloalkyl radicals, R2 is an unsubstituted orhalomethyl substituted alkylidine radical of up to 12 carbon atoms, andwherein R1 and R2 can, together with the carbon atom to which they areattached, form a halomethyl substituted aromatic ring, Y is hydrogen orhydroxy R(S-CH2-CHY-CH2X)2 (2) wherein X is halogen and R is-CH2-C6H5-CH2- or -CH2-CH=CH-CH2-, Y is hydrogen or hydroxy andC6H5-CH2-S-CH2-CHOH-CH2X. (3)
 12. A compound according to claim 11wherein X is chlorine.
 13. A compound according to claim 11, wherein Xis bromine.
 14. A compound of the formula in accordance with claim 11.15. A compound of the formula C6H5-CH2-S-CH2-CHOH-CH2Cl in accordancewith claim
 11. 16. Methallyl 3-chloro-propyl sulfide in accordance withclaim
 11. 17. 1,8-dichloro-5-thia-2-octene in accordance with claim 11.18. A haLogenated thioether according to claim 11 wherein Y is hydrogen.19. A halogenated thioether compound according to claim 11 wherein Y isOH.
 20. A process for the preparation of allyl 3-chloro-2-hydroxy-propylsulphide, which comprises reacting allyl chloride and 3-hydroxy-thietaneand recovering the sulphide product therefrom.
 21. Allyl3-chloro-2-hydroxy-propyl sulphide.